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Given an ODE of the form $$ay''(x)+by'(x)+cy(x)=f(x)$$

I know that we can find the general solution by finding the complementary function and particular solution and then adding them. My question is, why does this work?

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It works because this equation is linear in terms of $y$. To be precise, the differential operator $$P = a\frac{d^2}{dx^2} + b\frac{d}{dx} + cI,$$ acting on a space of twice differentiable functions is linear.

Therefore, if two functions $y_1$ and $y_2$ both solve the equation $$Py=f,$$then by taking the difference of their equations we get $$0 = f-f = Py_1 - Py_2=P(y_1-y_2),$$the latter equality being the critical part where the linearity of $P$ comes into play.

Therefore, all solutions of the initial differential equation differ by a solution of the corresponding homogenous equation. In other words, you can find a particular solution $y_p$, and then find a solution $y_h$ of the homogenous equation, then $y_p+y_h$ also solves the initial equation.